Mechanistic insight of in situ electrochemical reduction of solid PbO to lead in ChCl-EG deep eutectic solvent
Mechanistic insight of in situ electrochemical reduction of solid PbO to lead in ChCl-EG deep eutectic solvent
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固体 PbO 在 ChCl-EG 低共熔溶剂中原位电化学还原成铅的机理研究
DOI：
10.1016/j.electacta.2015.11.013
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发表时间：
2015-12
影响因子：
6.6
通讯作者：
Kai Gong
中科院分区：
文献类型：
--
作者：
Jian Li;Yan Li;Zhongren Zhou;Kai Gong
通过系统的研究，初步阐明了固体PbO在氯化胆碱-乙二醇低共熔溶剂（ChCl-EGDES）中的原位电还原机理。循环伏安测试表明，固体PbO可直接电化学还原为金属铅，增加扫描次数有利于还原过程。以PbO为阴极，石墨为阳极的恒电位电解表明，阳极产生的大量气体主要由O2和少量Cl 2组成，而阴极释放的H2优先吸附在还原的金属铅表面。部分Cl 2可以留在电解质中，并与之反应形成氧化性Cl− 3离子。在电解过程中，PbO（s）→ [PbO·Cl·EG]−→ Pb（s）的溶解-电沉积过程与PbO（s）→ Pb（s）的直接还原过程同时存在。ESI-MS分析表明，在还原过程前后，ChCl-EG-PbO溶液中分别形成了配阴离子[PbO·Cl·EG]−和[ChCl·O·EG]2−。提出了PbO在ChCl-EG DES中还原为金属铅的机理模型。原位电解过程最初发生在集电器/PbO/电解质3 PI处，然后新形成的Pb/PbO/电解质3 PI膨胀直到整个本体金属化。这些发现为从金属氧化物电化学生产金属和合金的含义和优化提供了科学深入的讨论基础。
The in situ electroreduction mechanism of solid PbO in choline chloride-ethylene glycol deep eutectic solvent (ChCl-EG DES) is preliminarily clarified through systematical investigations at cell voltage 2.5 V and 353 K. Cyclic voltammetry of the cavity microelectrode loaded with PbO powders exhibits that solid PbO can be direct electrochemically reduced to metallic lead and increasing scan numbers is beneficial to the deoxidation process. Potentiostatic electrolysis with an assumed cathode of PbO pellet and a graphite anode shows that generated numerous gases are mainly composed of O2with small amounts of Cl2at anode whereas H2is released and preferentially adsorbed on the surface of reduced metallic lead at cathode. Parts of Cl2can remain in the electrolyte and react with it to form oxidizing Cl−3ions. Besides, the dissolution-electrodeposition of PbO(s) → [PbO·Cl·EG]−→ Pb(s) exists simultaneously with the direct deoxidation of PbO(s) → Pb(s) during the electrolysis process. ESI-MS analysis implies that complex anions [PbO·Cl·EG]−and [ChCl·O·EG]2−are formed in ChCl-EG-PbO solution before and after the deoxidation process, respectively. Furthermore, a reduction mechanism model of PbO bulk to metallic lead in ChCl-EG DES is proposed. The in situ electrolysis process takes place initially at the current collector/PbO/electrolyte 3PIs and then new formed Pb/PbO/electrolyte 3PIs expands until the whole bulk are metallized. These findings provide a basis for scientifically in-depth discussion on the implication and optimization of the electrochemical production of metals and alloys from metal oxides.
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